JPH0689145B2 - Wholly aromatic copolymerized polyimide ester and its production method - Google Patents

Description

TECHNICAL FIELD The present invention relates to a thermoplastic wholly aromatic copolymerized polyimide ester having excellent dimensional stability and a method for producing the same. More specifically, the present invention relates to a novel polyimide ester suitably used for electric and electronic parts which require excellent dimensional stability and dimensional accuracy in both the flow direction (MD) and the direction perpendicular to it (TD), and a method for producing the same.

[Conventional technology]

In recent years, MD has come to be known as a thermoplastic resin having an extremely small linear expansion coefficient. These are a group of resins called thermotropic liquid crystal polymers, such as Japanese Patent Publication No. Sho 56-18011.
Examples thereof include wholly aromatic copolymerized polyimide esters described in JP-A No. 54-77691, JP-B No. 47-47870 and the like.

These polyesters have a small linear expansion coefficient in MD,
In TD, the linear expansion coefficient was comparable to that of ordinary thermoplastic resins, and it could not be said that the dimensional stability was sufficient.

Further, a polyimide ester having an imide bond and an ester bond in a polymer molecule is well known. For example, U.S. Pat.No. 3,527,311 has a high heat resistance, and JP-A-58-67725 has a heat resistance, mechanical properties, and improved workability. 84326 has a high elastic modulus, JP-A-58-113222 has a toughness, and JP-A-60-4531 has a high rigidity.
2-132931 to 132934, JP-A-63-57637 discloses that abrasion resistance, toughness, moldability, improved workability, these polyimide esters also have dimensional stability. It wasn't enough.

[Problems to be Solved by the Invention]

A first object of the present invention is to solve the above-mentioned problems and to provide a novel thermoplastic resin having excellent dimensional stability and dimensional accuracy in both MD and TD, and having excellent heat resistance and mechanical properties. A second object of the present invention is to provide a wholly aromatic copolymerized polyimide ester, and a practically particularly advantageous production of a thermoplastic wholly aromatic copolymerized polyimide ester having the above-mentioned excellent properties. To provide a method.

[Means for Solving the Problems]

The present inventors, as a result of repeated intensive research to solve the above problems, a specific phenylene-based aromatic repeating unit,
A specific biphenylene-based aromatic repeating unit and a specific trimellitimide imide-based aromatic repeating unit have a main chain structure that is linked by an ester bond at a specific ratio,
And the novel thermoplastic wholly aromatic copolymerized polyimide ester that has a specific melt viscosity is a polymer that is extremely excellent in dimensional stability and dimensional accuracy, as well as in heat resistance and mechanical properties. Heading out, the present invention has been completed.

That is, the present invention has the following formula The repeating unit (U-I) represented by The repeating unit (U-II) represented by (However, the two carbonyl groups in the formula [III] are located in the para position or the meta position with respect to each other.) And a repeating unit (U-III) represented by the following formula Of the repeating unit (U-IV), the repeating units (U-I), (U-II), (U-III) and (U-IV) are linked to each other by forming an ester bond. (U-I) is 20-90 mol%, (U-II) is 5-40%.
Mol%, (U-III) is 1.0 to 39.9 mol%, (U-IV) is
0.1 to 4.0 mol%, [(U-III) + (U-IV)] is 5 to 4
It is present in a proportion of 0 mol% and is (U-II) / [(U-III) +
(U-IV)] has a molar ratio of (10/11) to (11/10), a shear stress of 0.025 Mpa, and a melt viscosity at a temperature of 300 to 400 ° C. of 1.0 to 1.0 × 10 ⁵ Pa · s. A thermoplastic wholly aromatic copolymerized polyimide ester is provided. This polyimide ester has the following general formula (However, Y ¹ in the formula [I ′] is a hydrogen atom or R ¹ CO— (wherein R ¹ represents a hydrocarbon group having 1 to 18 carbon atoms), and Z ¹ is hydrogen. An atom or a hydrocarbon group having 1 to 18 carbon atoms) [I '] represented by the following general formula (However, Y ² in the formula [II ′] is a hydrogen atom or R ² CO—, and Y ³ is a hydrogen atom or R ³ CO—. Here, R ² and
R ³ represents a hydrocarbon group having 1 to 18 carbon atoms. ) And a compound of the following general formula (However, Z ² and Z ³ in the formula [III ′] are a hydrogen atom or a hydrocarbon group having 1 to 18 carbon atoms, and the —COOZ ² group and the —COOZ ³ group are mutually para-position or meta-position of the benzene ring. Compound [III ′] represented by the following general formula (However, Z ⁴ and Z ⁵ in the formula [IV ′] are a hydrogen atom or a hydrocarbon group having 1 to 18 carbon atoms.]
V ') and [I'] are 20 to 90 mol% and [II '] is 5 to 40
Mol%, [III '] 1.0 to 39.9 mol%, [IV'] 0.1
˜4.0 mol%, [III ′] + [IV ′] is 5˜40 mol%, and the molar ratio of [II ′] / ([III ′] + [IV ′]) is (1
011) reacted so that the ratio of ~ (11/10), the general formula Y ^p -O-Z ^q [V '] (wherein, the formula [V' Y ^p in], the Y ^1, Y ₂ or Y ³ and Z ^q represents Z ¹ , Z ² , Z ³ , Z ⁴ or Z ⁵ )), or a compound [V ′] represented by the following formula: General formula (However, Y ¹ in the formula [I ′] is a hydrogen atom or R ¹ CO— (wherein R ¹ represents a hydrocarbon group having 1 to 18 carbon atoms), and Z ¹ is hydrogen. An atom or a hydrocarbon group having 1 to 18 carbon atoms) [I '] represented by the following general formula (However, in the formula [II ′], Y ² is a hydrogen atom or R ² CO—, and Y ³ is a hydrogen atom or R ³ CO—. Here, R ² and
R ³ represents a hydrocarbon group having 1 to 18 carbon atoms. ) And a compound of the following general formula (However, Z ² and Z ³ in the formula [III ′] are a hydrogen atom or a hydrocarbon group having 1 to 18 carbon atoms, and the —COOZ ² group and the —COOZ ³ group are mutually para-position or meta-position of the benzene ring. Compound [III ′] represented by the following general formula (However, Z ⁴ and Z ⁵ in the formula [IV ″] are a hydrogen atom or a hydrocarbon group having 1 to 18 carbon atoms, and the —COOZ ⁴ group and the —COOZ ⁵ group are in the para position or meta to the amide group. The compound [IV ″] represented by the formula (1) is 20 to 90 mol% of [I ′],
I ′] is 5 to 40 mol%, [III ′] is 1.0 to 39.9 mol%,
[IV ″] is 0.1 to 4.0 mol%, and [III ′] + [I
V ″] is 5 to 40 mol%, [II ′] / ([III ′] + [I
V ″]) is reacted at a molar ratio of (10/11) to (11/10), and imide cyclization of compound [IV ″] and the following general formula Y ^p —O—Z ^q [V ′ (However, Y ^p in the formula [V ′] represents Y ¹ , Y ² or Y ³ and Z ^q represents Z ¹ , Z ² , Z ³ , Z ⁴ or Z ^5. ) The compound [V '] represented can be practically advantageously produced by elimination.

In the polyimide ester of the present invention, it is important that the aromatic ring of the repeating unit (U-II) is only a diphenylene group, and the polyimide ester obtained when the aromatic ring contains a phenylene group is a molded product. Burns are observed, strength and elastic modulus are significantly reduced, and dimensional stability and dimensional accuracy are also reduced.

The repeating unit (U-IIII) is specifically Is.

In addition, the polyimide ester in the present invention may have any one of these, or may have both at an arbitrary ratio.

The repeating units (U-I), (U-II), (U-III) and (U-I) which constitute the copolymer according to the present invention.
The ratio of V) is within the range of the above molar ratio. These repeating units form an ester bond and are randomly linked.

If the ratio of the repeating unit is out of the range of the above molar ratio, desired dimensional stability and dimensional accuracy may not be sufficiently satisfied. If the ratio of (U-IV) exceeds 4.0 mol%, the moldability will be significantly reduced.

The melt viscosity of the copolymer according to the present invention under the above conditions is within the above range. When the melt viscosity is out of the above range, the thermoplasticity becomes insufficient and molding by injection molding or the like cannot be made sufficiently easy, or the mechanical properties become insufficient and desired heat resistance is obtained. May not be fully satisfied.

There is no particular limitation as a general production method of the thermoplastic wholly aromatic copolymerized polyimide ester of the present invention, but usually,
It can be suitably manufactured by the above-mentioned manufacturing method. Next, this manufacturing method will be described in detail.

R ¹ , R ² and R ³ are each a hydrocarbon group having 1 to 18 carbon atoms, and specific examples of the hydrocarbon group include, for example, methyl group, ethyl group, n-propyl group and isopropyl group. , N
-Butyl group, sec-butyl group, tert-butyl group, pentyl group, isopentyl group, neopentyl group, heptyl group,
Alkyl group such as isooctyl group, nonyl group, decyl group, pentadecyl group, heptadecyl group, cycloalkyl group such as cyclopentyl group and cyclohexyl group, aryl group or aralkyl group such as phenyl group, tolyl group, naphthyl group and benzyl group Can be mentioned. Of these, a methyl group is particularly preferable.

It should be noted that R ¹ , R ² and R ³ may all be the same, or some of them may be the same and the others may be different, or all may be different from each other. May be.

Wherein ^{Z 1, Z 2, Z 3} , Z 4 and Z ⁵ is each hydrogen atom or a hydrocarbon group having 1 to 18 carbon atoms, and specific examples of the hydrocarbon group, the above-exemplified various carbide A hydrogen group etc. can be mentioned. Particularly preferred as Z ¹ , Z ² , Z ³ , Z ⁴ and Z ⁵ are a hydrogen atom and a methyl group. In addition, Z ¹ , Z ² ,
Z ³ , Z ⁴ , and Z ⁵ may all be the same, or only some may be the same as each other, or all may be different. Particularly preferred are a hydrogen atom and a methyl group.

As the compound [I '], 4-hydroxybenzoic acid or R ¹ COOH (wherein R ¹ is the same as above) is used.
Alternatively, 4-acyloxybenzoic acid obtained by acylation with a derivative thereof, or 4-hydroxybenzoic acid or the 4-acyloxybenzoic acid is esterified with Z ¹ OH (where Z ¹ is the same as above). The following 4-hydroxybenzoic acid ester or 4-acyloxybenzoic acid ester can be mentioned.

Specific examples of the compound [I '] include 4-hydroxybenzoic acid, methyl 4-hydroxybenzoate, and 4
4-hydroxybenzoic acid esters such as ethyl-hydroxybenzoate, propyl 4-hydroxybenzoate, butyl 4-hydroxybenzoate and benzyl 4-hydroxybenzoate, 4-acetoxybenzoic acid, 4-benzoyloxybenzoic acid and the like 4 Examples include 4-acyloxybenzoic acid esters such as -acyloxybenzoic acid, methyl 4-acetoxybenzoate, butyl 4-acetoxybenzoate, and benzyl 4-acetoxybenzoate.

Among these, 4-hydroxybenzoic acid, methyl 4-hydroxybenzoate, 4-acetoxybenzoic acid, methyl 4-acetoxybenzoate and the like are preferable, and 4-hydroxybenzoic acid and 4-acetoxybenzoic acid are particularly preferable.

In addition, these compounds may be used individually by 1 type, or may use 2 or more types together.

The compound [II ′] is 4,4′-dihydroxyphenyl, or R ² COOH or R ³ COOH (provided that R ² and R ³ are the same as defined above) or a compound thereof. A compound obtained by acylating a derivative may be mentioned.

Specific examples of the compound [II ′] include, for example, 4,4 ′
4'-acyloxy-4-hydroxybiphenyl such as -dihydroxyphenyl, 4'-acetoxy-4-hydroxybiphenyl and 4,4'-diacyloxybiphenyl such as 4,4'-diacetoxybiphenyl. Among these, 4,4'-dihydroxybiphenyl and 4,4'-diacetoxybiphenyl are preferable.

In addition, these compounds may be used individually by 1 type, or may use 2 or more types together.

Examples of the compound [III ′] include terephthalic acid, isophthalic acid or Z ² OH or Z ³ OH (provided that Z ² and
Z ³ is the same as above. And a compound formed by esterification.

Specific examples of the compound [III ′] include monoterephthalic acid such as terephthalic acid, isophthalic acid, monomethyl terephthalate, monoethyl terephthalate, monopropyl terephthalate, monobutyl terephthalate, monohexyl terephthalate and monobenzyl terephthalate. Ester, dimethyl terephthalate, terephthalic acid diester such as diethyl terephthalate, monomethyl isophthalate,
Monoethyl isophthalate, monopropyl isophthalate,
Monobutyl isophthalate, monohexyl isophthalate,
Monooctyl isophthalate, monodecyl isophthalate,
Isophthalic acid monoester such as monobenzyl isophthalate, dimethyl isophthalate, diethyl isophthalate,
Mention may be made of isophthalic acid diesters such as dibutyl isophthalate. Among these, terephthalic acid,
Dimethyl terephthalate, isophthalic acid, dimethyl isophthalate and the like are preferable, and terephthalic acid and isophthalic acid are particularly preferable.

In addition, these compounds may be used individually by 1 type, or 2 or more types may be used together as a mixture.

As the compound [IV ″], for example, The compound represented by These may be used alone or in combination of two or more.

As the method for producing the compound [IV ′], for example, the following formula A trimellitic acid derivative (Z is Z ⁴ or Z ⁵ , which are the same as those described above, and Z ⁴ and Z ⁵ are usually the same), and a general formula The amic acid represented by the above general formulas [IV ″ a], [IV ″ b] and [IV ″ c] is produced by the reaction with p-phenylenediamine represented by the following formula: Then, this is dehydrated and cyclized. As a result, the trimellitimide compound of [IV '] can be obtained.

When the above method is used, the compound [IV ″] is
Usually, the above general formulas [IV ″ a], [IV ″ b] and [IV ″
Obtained as a mixture of compounds represented by c].

The compound [IV ′] can be obtained, for example, by subjecting the compound [IV ″] synthesized as described above to dehydration cyclization (imide cyclization).

The compound [IV ″] can also be obtained by hydrolyzing the compound [IV ′].

The reaction between the compound [A] and the compound [B] easily proceeds by mixing both components, preferably in a solution state, to produce a sparingly soluble amic acid, that is, the compound [IV ″], which is usually The reaction proceeds sufficiently efficiently at room temperature, but the preferred reaction temperature is
The temperature is in the range of −50 ° C. to 100 ° C., and is often 0 to 80 ° C. This reaction proceeds in a short time and usually does not require the presence of a special catalyst.

Various methods are used for the dehydration cyclization of the compound [IV ″]. Specific examples include a method of dehydration cyclization in the presence of a carboxylic acid anhydride, an inorganic acid having a dehydrating action, or Examples thereof include a method of dehydroxylation with the condensate, a method of azeotropic dehydration cyclization in the presence of an acid catalyst, a cyclization method using a special dehydrating agent, and a dehydration cyclization method by heating.

In addition, in the compound (IV ′), those in which Z ⁴ and Z ⁵ are groups other than hydrogen atom can also be obtained by a reaction using a starting material of the compound [IV ″] having a corresponding substituent. Alternatively, it can be derived from the compound [IV ′] in which Z ⁴ and Z ⁵ are hydrogen atoms.

Further, the compounds [I ′], [II ′], [III ′] and [I
V ′], when Y ¹ , Y ² , Y ³ , Z ¹ , Z ² , Z ³ , Z ⁴ and Z ⁵ are all groups other than hydrogen atom, these compounds are individually synthesized. May be used, or they may be simultaneously synthesized.

The compounds, [I '], [II'], [III '] and [I
V '] reaction is usually 200 ~ 400 ℃, preferably 230 ~ 370
It is carried out at a temperature of ° C and usually below atmospheric pressure, and in the latter half stage of polycondensation, preferably at a vacuum degree of 300 to 0.01 Torr. The reaction time is usually several minutes to several tens hours depending on the melt viscosity of the target polymer. In order to avoid deterioration of the polymer at the reaction temperature, it is preferably several minutes to several hours.

A catalyst is not particularly required for the above reaction, but a suitable polycondensation catalyst such as antimony oxide or germanium oxide can be used.

Regarding the timing of adding the reaction raw materials, all reaction raw materials may be mixed in the first stage to carry out the reaction. For example, compound [I '], compound [II'], [III '] and [IV'] ], The reaction time may be changed. As a result, the composition distribution of the polyimide ester can be easily controlled, and random copolyester and block copolyester can be arbitrarily controlled.

The compounds [I '], [II'], [III '] and [I]
The reaction of V ″] is carried out by the above-mentioned compounds [I ′], [II ′],
In the reaction of [III '] and [IV'], the compound [I
It can be carried out in the same manner except that V ′] is replaced with the compound [IV ″] and imide cyclization is also carried out.

The above reaction is usually carried out without using a special solvent, but if desired, it may be carried out using a suitable solvent.

The polyimide ester according to the present invention can be synthesized as described above. The synthesized polymer can be subjected to a post-treatment such as a known purification operation, if desired, to be recovered in a desired purity.

The polyimide ester according to the present invention can be suitably produced as described above.

The polyimide ester according to the present invention can be injection-molded at a normal molding temperature (400 ° C or lower), and any molding method used for general thermoplastic resins such as extrusion molding, compression molding, and spinning is possible. Is. Further, the molded product can be heat-treated at a suitable temperature for a suitable time.
Therefore, the polyimide ester according to the present invention is a novel thermoplastic polymer having extremely excellent dimensional stability and dimensional accuracy in both MD and TD, and also excellent in heat resistance and mechanical properties, for example, heat resistance. It is useful as a material in various fields such as precision injection-molded parts for electric and electronic parts, filaments, films, sheets, etc., which require high dimensional accuracy.

〔Example〕

(Synthesis example) Synthesis of Trimellitic anhydride 69.17 g (0.36 mol) and p-phenylenediamine 19.47 g (0.18 mol) were dissolved in 200 ml of dimethylformamide (DMF), and DMF was refluxed. Immediately after the reflux was started, yellow powder crystals started to precipitate. After refluxing for 2.5 hours, it was cooled. The product was filtered, and the crystals were washed with DMF, then with acetone, and then dried to obtain the desired imide compound [IV'-1]. Elemental analysis theoretical value (measured value): C63.2 (63.3), H2.65 (2.61), N6.14 (6.17).

Example 1 0.024 mol (4.611 g) of trimellitic anhydride, 0.012 mol (1.298 g) of p-phenylenediamine and 100 ml of methyl ethyl ketone were placed in a 500 ml separable flask, and the mixture was stirred at room temperature for 1 hour. ] ([IV ″] Z ⁴ and Z ⁵ =
A precipitate of H) was formed.

Then, p-hydroxybenzoic acid 0.720 mol (99.45 g) 4,4'-dihydroxybiphenyl 0.240 mol (44.69 g), terephthalic acid 0.192 mol (31.90 g), isophthalic acid 0.036 mol (5.981 g), and acetic anhydride 1.200 mol. (112.8 ml) was charged, the temperature was raised to 150 ° C. with stirring under a nitrogen stream, and acetic anhydride was refluxed for 1 hour. Then in 90 minutes
The temperature was raised to 360 ° C., methyl ethyl ketone, water and acetic acid were distilled off, and dehydration cyclization and polymerization of amic acid proceeded.
After that, the pressure inside the system was reduced to 10 torr for 10 minutes, then 2t.
Polymerization was continued for 10 minutes under a reduced pressure of orr. The obtained polymer was taken out in a molten state.

The elemental analysis of the obtained polymer was as follows.

The IR spectrum of the obtained polymer is shown in FIG.

From these results and the like, it was confirmed that this polymer was a polyimide ester having a repeating unit and a composition represented by the following formula. The number in the formula represents the mol% of the repeating unit in the copolymer (same in the following examples and comparative examples).

Koka type flow tester (Shimadzu flow tester, CFT-50
0) with a diameter of 1.0 mm and L / D = 10 with a die of 10 kgf / c
The melt viscosity of this polymer was measured at a heating rate of 5 ° C./min at an extrusion pressure of m ² and found to be 280 ° C.
It was Pa · s.

This polymer exhibited optical anisotropy even in the molten state. The optical anisotropy was observed using a Nikon polarization microscope with a hot stage manufactured by Rincom.

Example 2 0.072 mol (13.83 g) of trimellitic anhydride, 0.036 mol (3.894 g) of P-phenylenediamine and 100 ml of methyl ethyl ketone were placed in a separable flask of 500 ml, and the mixture was stirred at room temperature for 1 hour. ] ([IV ″] Z ⁴ and Z ⁵ =
A precipitate of H) was formed.

Then, p-hydroxybenzoic acid 0.720 mol (99.45 g), 4,4'-dihydroxybiphenyl 0.240 mol (44.69 g), terephthalic acid 0.144 mol (23.92 g), isophthalic acid 0.060 mol (9.968 g) and acetic anhydride 1.200 mol. (112.8 ml) was charged, the temperature was raised to 150 ° C. with stirring under a nitrogen stream, and acetic anhydride was refluxed for 1 hour. Then in 90 minutes
The temperature was raised to 360 ° C., methyl ethyl ketone, water and acetic acid were distilled off, and dehydration cyclization and polymerization of amic acid proceeded.
After that, the pressure inside the system was reduced to 10 torr for 10 minutes, then 2t.
Polymerization was continued for 10 minutes under a reduced pressure of orr. The obtained polymer was taken out in a molten state.

The elemental analysis of the obtained polymer was as follows.

From these results and the like, it was confirmed that this polymer was a polyimide ester having a repeating unit and a composition represented by the following formula.

The melt viscosity of this polymer was measured by the same test method as in Example 1, and as a result, it was 350 Pa · s at 380 ° C. Also,
This polymer exhibited optical anisotropy even in the molten state.

Example 3 0.096 mol (18.44 g) of trimellitic anhydride, 0.048 mol (5.192 g) of P-phenylenediamine and 100 ml of methyl ethyl ketone were placed in a separable flask of 500 ml, and the mixture was stirred at room temperature for 1 hour. ] ([IV ″] Z ⁴ , Z ⁵ = H)
A precipitate was formed.

Then, p-hydroxybenzoic acid 0.720 mol (99.45 g) 4,4'-dihydroxybiphenyl 0.240 mol (44.69 g), terephthalic acid 0.132 mol (21.93 g), isophthalic acid 0.060 mol (9.968 g) and acetic anhydride 1.200 mol ( 112.8 ml) was added, the temperature was raised to 150 ° C. with stirring under a nitrogen stream, and acetic anhydride was refluxed for 1 hour. Then in 90 minutes
The temperature was raised to 360 ° C., methyl ethyl ketone, water and acetic acid were distilled off, and dehydration cyclization and polymerization of amic acid proceeded.
After that, the pressure inside the system was reduced to 10 torr for 10 minutes, then 2t.
Polymerization was continued for 10 minutes under a reduced pressure of orr. The obtained polymer was taken out in a molten state.

The elemental analysis of the obtained polymer was as follows.

From these results and the like, it was confirmed that this polymer was a polyimide ester having a repeating unit and a composition represented by the following formula.

The melt viscosity of this polymer was measured by the same test method as in Example 1 and found to be 380 Pa · s at 380 ° C. Also,
This polymer exhibited optical anisotropy in the molten state.

Example 4 0.072 mol (13.83 g) of trimellitic anhydride, 0.036 mol (3.894 g) of P-phenylenediamine and 100 ml of methyl ethyl ketone were placed in a separable flask of 500 ml, and the mixture was stirred at room temperature for 1 hour. ] ([IV ″] Z ⁴ , Z ⁵ = H)
A precipitate was formed.

Then, p-hydroxybenzoic acid 0.600 mol (82.87g), 4,4'-dihydroxybiphenyl 0.300 mol (55.87g), terephthalic acid 0.204 mol (33.89g), isophthalic acid 0.060 mol (9.968g) and acetic anhydride 1.200 mol. (112.8 ml) was charged, the temperature was raised to 150 ° C. with stirring under a nitrogen stream, and acetic anhydride was refluxed for 1 hour. Then in 90 minutes
The temperature was raised to 360 ° C., methyl ethyl ketone, water and acetic acid were distilled off, and dehydration cyclization and polymerization of amic acid proceeded.
After that, the pressure inside the system was reduced to 10 torr for 10 minutes, then 2t.
Polymerization was continued for 10 minutes under a reduced pressure of orr. The obtained polymer was taken out in a molten state.

The elemental analysis of the obtained polymer was as follows.

From these results and the like, it was confirmed that this polymer was a polyimide ester having a repeating unit and a composition represented by the following formula.

The melt viscosity of this polymer was measured by the same test method as in Example 1, and as a result, it was 330 Pa · s at 380 ° C. Also,
This polymer exhibited optical anisotropy in the molten state.

Example 5 0.072 mol (13.83 g) of trimellitic anhydride, 0.036 mol (3.894 g) of P-phenylenediamine and 100 ml of methyl ethyl ketone were placed in a separable flask of 500 ml, and the mixture was stirred at room temperature for 1 hour. ] ([IV ″] Z ⁴ , Z ⁵ = H)
A precipitate was formed.

Then, p-hydroxybenzoic acid 0.840 mol (116.0 g), 4,4'-dihydroxybiphenyl 0.180 mol (33.52 g), terephthalic acid 0.084 mol (13.95 g), isophthalic acid 0.060 mol (9.968 g) and acetic anhydride 1.200 mol. (112.8 ml) was charged, the temperature was raised to 150 ° C. with stirring under a nitrogen stream, and acetic anhydride was refluxed for 1 hour. Then in 90 minutes
The temperature was raised to 360 ° C., methyl ethyl ketone, water and acetic acid were distilled off, and dehydration cyclization and polymerization of amic acid proceeded.
After that, the pressure inside the system was reduced to 10 torr for 10 minutes, then 2t.
Polymerization was continued for 10 minutes under a reduced pressure of orr. The obtained polymer was taken out in a molten state.

The elemental analysis of the obtained polymer was as follows.

From these results and the like, it was confirmed that this polymer was a polyimide ester having a repeating unit and a composition represented by the following formula.

The melt viscosity of this polymer was measured by the same test method as in Example 1, and as a result, it was 310 Pa · s at 380 ° C. Also,
This polymer exhibited optical anisotropy in the molten state.

Example 6 P-hydroxybenzoic acid 0.720 mol (99.45 g), 4,4'-dihydroxybiphenyl 0.240 mol (44.69 g), terephthalic acid 0.144 mol (23.92 g), isophthalic acid 0.060 mol (9.96 g), compound [IV '-1] 0.036 mol (16.43) and 1.200 mol (112.8 ml) of acetic anhydride were added, the temperature was raised to 150 ° C with stirring under a nitrogen stream, and the acetic anhydride was refluxed for 1 hour. Then in 90 minutes
The temperature was raised to 360 ° C., acetic acid was distilled off, and polymerization was allowed to proceed. Then, the pressure inside the system was reduced to 10 torr, and the polymerization was continued for 10 minutes and further reduced pressure to 2 torr for 10 minutes. The obtained polymer was taken out in a molten state.

The elemental analysis of the obtained polymer was as follows.

From these results and the like, it was confirmed that this polymer was a polyimide ester having a repeating unit and a composition represented by the following formula.

The melt viscosity of this polymer was measured by the same test method as in Example 1, and as a result, it was 350 Pa · s at 380 ° C. Also,
This polymer exhibited optical anisotropy in the molten state.

Example 7 p-acetoxybenzoic acid 0.720 mol (129.7 g), 4,4'-diacetoxybiphenyl 0.240 mol (64.87 g), terephthalic acid 0.144 mol (23.92 g), isophthalic acid 0.060 mol (9.96 g) and compound [ IV′-1] 0.036 mol (16.43 g was added, the temperature was raised to 360 ° C. for 90 minutes while stirring under a nitrogen stream, the acetic acid was distilled off, and the polymerization was allowed to proceed.
Polymerization was continued for 10 minutes at a reduced pressure of 2 torr and further for 10 minutes at a reduced pressure of 2 torr. The obtained polymer was taken out in a molten state.

The elemental analysis of the obtained polymer was as follows.

From these results and the like, it was confirmed that this polymer was a polyimide ester having a repeating unit and a composition represented by the following formula.

The melt viscosity of this polymer was measured by the same test method as in Example 1, and as a result, it was 355 Pa · s at 380 ° C. Also,
This polymer exhibited optical anisotropy in the molten state.

Comparative Example 1 0.720 mol (129.7 g) of p-acetoxybenzoic acid, 0.240 mol (64.87 g) of 4,4'-diacetoxybiphenyl, 0.180 mol (29.90 g) of terephthalic acid, and 0.060 mol (9.968 g) of isophthalic acid were added. Then, the temperature was raised to 360 ° C. in 90 minutes while stirring under a nitrogen stream, the acetic acid was distilled off, and the polymerization was allowed to proceed. After that, the pressure inside the system was reduced to 10 torr for 10 minutes, then 2 torr.
The polymerization was continued under reduced pressure for 10 minutes. The obtained polymer was taken out in a molten state.

The elemental analysis of the obtained polymer was as follows.

From these results and the like, it was confirmed that this polymer was a polyimide ester having a repeating unit and a composition represented by the following formula.

The melt viscosity of this polymer was 100 Pa · s at 330 ° C. as measured by the same test method as in Example 1. Also,
This polymer exhibited optical anisotropy in the molten state.

Comparative Example 2 0.120 mol (23.06 g) of trimellitic anhydride, 0.060 mol (6.488 g) of p-phenylenediamine and 100 ml of methyl ethyl ketone were placed in a 500 ml separable flask, and the mixture was stirred at room temperature for 1 hour. ] ([IV ″] Z ⁴ , Z ⁵ = H)
A precipitate was formed.

Then, p-hydroxybenzoic acid 0.720 mol (99.45g), 4,4'-dihydroxybiphenyl 0.240 mol (44.69g), terephthalic acid 0.120 mol (19.94g), isophthalic acid 0.060 mol (9.968g) and acetic anhydride 1.200 mol. (112.8 ml) was charged, the temperature was raised to 150 ° C. with stirring under a nitrogen stream, and acetic anhydride was refluxed for 1 hour. Then in 90 minutes
The temperature was raised to 360 ° C., methyl ethyl ketone, water and acetic acid were distilled off, and dehydration cyclization and polymerization of amic acid proceeded.
After that, the pressure inside the system was reduced to 10 torr for 10 minutes, then 2t.
Polymerization was continued for 10 minutes under a reduced pressure of orr. The obtained polymer was taken out in a molten state.

The elemental analysis of the obtained polymer was as follows.

From these results and the like, it was confirmed that this polymer was a polyimide ester having a repeating unit and a composition represented by the following formula.

The melt viscosity of this polymer was measured by the same test method as in Example 1, and as a result, it did not melt up to 400 ° C. Also,
The polymer could not be injection molded.

Comparative Example 3 0.120 mol (23.06 g) of trimellitic anhydride, 0.060 mol (6.488 g) of p-phenylenediamine and 100 ml of methyl ethyl ketone were placed in a 500 ml separable flask, and the mixture was stirred at room temperature for 1 hour. ] ([IV ″] Z ⁴ , Z ⁵ = H)
A precipitate was formed.

Then, p-hydroxybenzoic acid 0.720 mol (99.45g), 4,4'-dihydroxybiphenyl 0.240 mol (44.69g), terephthalic acid 0.060 mol (9.968g), isophthalic acid 0.120 mol (19.94g) and acetic anhydride 1.200 mol. (112.8 ml) was charged, the temperature was raised to 150 ° C. with stirring under a nitrogen stream, and acetic anhydride was refluxed for 1 hour. Then in 90 minutes
The temperature was raised to 360 ° C., methyl ethyl ketone, water and acetic acid were distilled off, and dehydration cyclization and polymerization of amic acid proceeded.
After that, the pressure inside the system was reduced to 10 torr for 10 minutes, then 2t.
Polymerization was continued for 10 minutes under a reduced pressure of orr. The obtained polymer was taken out in a molten state.

The elemental analysis of the obtained polymer was as follows.

From these results and the like, it was confirmed that this polymer was a polyimide ester having a repeating unit and a composition represented by the following formula.

The melt viscosity of this polymer was 100 Pa · s at 330 ° C. as measured by the same test method as in Example 1. Also,
This polymer exhibited optical anisotropy in the molten state.

Comparative Example 4 trimellitic anhydride 0.120 mol (23.06 g), 4,4'-diaminophenyl ether 0.060 mol (12.01 g)
Then, 100 ml of methyl ethyl ketone was placed in a 500 ml separable flask, and the mixture was stirred at room temperature for 1 hour to give the compound [IV ″ -1] A precipitate of the compound substituted in was formed.

Then, p-hydroxybenzoic acid 0.720 mol (99.45g), 4,4'-dihydroxybiphenyl 0.240 mol (44.69g), terephthalic acid 0.120 mol (19.94g), isophthalic acid 0.060 mol (9.968g) and acetic anhydride 1.200 mol. (112.8 ml) was charged, the temperature was raised to 150 ° C. with stirring under a nitrogen stream, and acetic anhydride was refluxed for 1 hour. Then in 90 minutes
The temperature was raised to 360 ° C., methyl ethyl ketone, water and acetic acid were distilled off, and dehydration cyclization and polymerization of amic acid proceeded.
After that, the pressure inside the system was reduced to 10 torr for 10 minutes, then 2t.
Polymerization was continued for 10 minutes under a reduced pressure of orr. The obtained polymer was taken out in a molten state.

The elemental analysis of the obtained polymer was as follows.

From these results and the like, it was confirmed that this polymer was a polyimide ester having a repeating unit and a composition represented by the following formula.

The melt viscosity of this polymer was measured by the same test method as in Example 1, and as a result, it was 300 Pa · s at 330 ° C. Also,
This polymer exhibited optical anisotropy in the molten state.

Comparative Example 5 0.120 mol (23.06 g) of trimellitic anhydride, 0.060 mol (6.488 g) of m-phenylenediamine and 100 ml of methyl ethyl ketone were placed in a separable flask of 500 ml, and the mixture was stirred at room temperature for 1 hour. 〕of A precipitate of the compound substituted in was formed.

Then, p-hydroxybenzoic acid 0.720 mol (99.45g), 4,4'-dihydroxybiphenyl 0.240 mol (44.69g), terephthalic acid 0.120 mol (19.94g), isophthalic acid 0.060 mol (9.968g) and acetic anhydride 1.200 mol. (112.8 ml) was charged, the temperature was raised to 150 ° C. with stirring under a nitrogen stream, and acetic anhydride was refluxed for 1 hour. Then in 90 minutes
The temperature was raised to 360 ° C., methyl ethyl ketone, water and acetic acid were distilled off, and dehydration cyclization and polymerization of amic acid proceeded.
After that, the pressure inside the system was reduced to 10 torr for 10 minutes, then 2t.
Polymerization was continued for 10 minutes under a reduced pressure of orr. The obtained polymer was taken out in a molten state.

The elemental analysis of the obtained polymer was as follows.

From these results and the like, it was confirmed that this polymer was a polyimide ester having a repeating unit and a composition represented by the following formula.

The melt viscosity of this polymer was measured by the same test method as in Example 1, and as a result, it was 330 Pa · s at 300 ° C. Also,
This polymer exhibited optical anisotropy in the molten state.

Comparative Example 6 0.072 mol (13.83 g) of trimellitic anhydride, 0.036 mol (3.894 g) of p-phenylenediamine and 100 ml of methyl ethyl ketone were placed in a separable flask of 500 ml, and the mixture was stirred at room temperature for 1 hour. ] ([IV ″] Z ⁴ , Z ⁵ = H)
A precipitate was formed.

Then, p-hydroxybenzoic acid 0.720 mol (99.45 g), 4,4'-dihydroxybiphenyl 0.218 mol (40.60 g), hydroquinone 0.022 mol (2.422 g), terephthalic acid 0.144 mol (23.92 g), isophthalic acid 0.060 mol ( 9.968 g) and 1.200 mol (112.8 ml) of acetic anhydride were added, the temperature was raised to 150 ° C. with stirring under a nitrogen stream, and the acetic anhydride was refluxed for 1 hour. Then in 90 minutes
The temperature was raised to 360 ° C., methyl ethyl ketone, water and acetic acid were distilled off, and dehydration cyclization and polymerization of amic acid proceeded.
After that, the pressure inside the system was reduced to 10 torr for 10 minutes, then 2t.
Polymerization was continued for 10 minutes under a reduced pressure of orr. The obtained polymer was taken out in a molten state.

The elemental analysis of the obtained polymer was as follows.

From these results and the like, it was confirmed that this polymer was a polyimide ester having a repeating unit and a composition represented by the following formula.

The melt viscosity of this polymer was measured by the same test method as in Example 1, and as a result, it was 500 Pa · s at 380 ° C. Also,
This polymer exhibited optical anisotropy in the molten state. Also,
Burns were observed on the molded product.

Comparative Example 7 0.072 mol (13.83 g) of trimellitic anhydride, 0.036 mol (7.21 g) of 4,4'-diaminophenyl ether
Then, 100 ml of methyl ethyl ketone was placed in a 500 ml separable flask, and the mixture was stirred at room temperature for 1 hour to obtain the compound [IV ″ -1] A precipitate of the compound substituted in was formed.

Then, p-hydroxybenzoic acid 0.720 mol (99.45 g), 4,4'-dihydroxybiphenyl 0.218 mol (40.60 g), hydroquinone 0.022 mol (2.422 g), terephthalic acid 0.144 mol (23.92 g), isophthalic acid 0.060 mol ( 9.968 g) and 1.200 mol (112.8 ml) of acetic anhydride were added, the temperature was raised to 150 ° C. with stirring under a nitrogen stream, and the acetic anhydride was refluxed for 1 hour. Then in 90 minutes
The temperature was raised to 360 ° C., methyl ethyl ketone, water and acetic acid were distilled off, and dehydration cyclization and polymerization of amic acid proceeded.
After that, the pressure inside the system was reduced to 10 torr for 10 minutes, then 2t.
Polymerization was continued for 10 minutes under a reduced pressure of orr. The obtained polymer was taken out in a molten state.

The elemental analysis of the obtained polymer was as follows.

From these results and the like, it was confirmed that this polymer was a polyimide ester having a repeating unit and a composition represented by the following formula.

The melt viscosity of this polymer was measured by the same test method as in Example 1 and was found to be 200 Pa · s at 380 ° C. Also,
This polymer exhibited optical anisotropy in the molten state. Also,
Burns were observed in the molded product.

Comparative Example 8 0.072 mol (13.83 g) of trimellitic anhydride, 0.036 mol (7.21 g) of 4,4'-diaminophenyl ether
Then, 100 ml of methyl ethyl ketone was placed in a 500 ml separable flask, and the mixture was stirred at room temperature for 1 hour to obtain the compound [IV ″ -1] A precipitate of the compound substituted in was formed.

Then, p-hydroxybenzoic acid 0.720 mol (99.45 g) 4,4'-dihydroxybiphenyl 0.240 mol (44.69 g), terephthalic acid 0.144 mol (23.92 g), isophthalic acid 0.060 mol (9.968 g) and acetic anhydride 1.200 mol ( 112.8 ml) was added, the temperature was raised to 150 ° C. with stirring under a nitrogen stream, and acetic anhydride was refluxed for 1 hour. Then in 90 minutes
The temperature was raised to 360 ° C., methyl ethyl ketone, water and acetic acid were distilled off, and dehydration cyclization and polymerization of amic acid proceeded.
After that, the pressure inside the system was reduced to 10 torr for 10 minutes, then 2t.
Polymerization was continued for 10 minutes under a reduced pressure of orr. The obtained polymer was taken out in a molten state.

The elemental analysis of the obtained polymer was as follows.

From these results and the like, it was confirmed that this polymer was a polyimide ester having a repeating unit and a composition represented by the following formula.

The melt viscosity of this polymer was measured by the same test method as in Example 1 and was found to be 300 Pa · s at 320 ° C. Also,
This polymer exhibited optical anisotropy in the molten state.

Table 1 shows the linear expansion coefficient, molding shrinkage ratio, bending property, and heat distortion temperature of the polymers of Examples 1 to 7 and Comparative Examples 1 to 8.

In addition, the measurement of these characteristics was performed as follows.

Molding of Test Piece Each polymer was molded using an injection molding machine (Toshiba IS45P) at a molding temperature of 250 to 390 ° C and a mold temperature of 120 ° C.

Measuring method 1. Coefficient of linear expansion 63.5 using Seiko thermal analyzer SSC-300 and TMA-100
Approximately 10 (measurement method) from the center of a 63.5 × 1.6 mm flat plate ×
The test piece cut out into 5 × 1.6 mm was measured in a compression mode at a load of 5 g and a heating rate of 10 ° C./min.

2. Molding shrinkage ratio MD and TD of the above flat plate were calculated by the following formula.

3. Bending characteristics Using a HTM250 manufactured by Toyo Seiki Co., Ltd., a 127 × 12.7 × 3.2 mm test piece was measured at 23 ° C.

Other test conditions were in accordance with ASTM D790.

4. Heat distortion temperature Using a device manufactured by Toyo Seiki Co., Ltd., a test piece of 127 × 12.7 × 3.2 mm was used and the load was measured at 18.6 kg / cm ² .

Other test conditions were in accordance with ASTM D648.

Effects of the Invention According to the present invention, both MD and TD have extremely excellent dimensional stability,
It is possible to provide a wholly aromatic copolymerized polyimide ester which is a novel thermoplastic polymer having dimensional accuracy and excellent in heat-resistant mechanical properties and the like, and a production method particularly advantageous in practical use thereof.

[Brief description of drawings]

FIG. 1 shows the IR of the polyimide ester obtained in Example 1.
It is a chart which shows a spectrum.

Claims (3)

[Claims] 1. The following formula The repeating unit (U-I) represented by The repeating unit (U-II) represented by (However, the two carbonyl groups in the formula [III] are located in the para position or the meta position with respect to each other.) And a repeating unit (U-III) represented by the following formula Of the repeating unit (U-IV), the repeating units (U-I), (U-II), (U-III) and (U-IV) are linked to each other by forming an ester bond. (U-I) is 20-90 mol%, (U-II) is 5-40%.
Mol%, (U-III) is 1.0 to 39.9 mol%, (U-IV) is
0.1 to 4.0 mol%, [(U-III) + (U-IV)] is 5 to 4
It is present in a proportion of 0 mol% and is (U-II) / [(U-III) +
(U-IV)] has a molar ratio of (10/11) to (11/10), a shear stress of 0.025 Mpa, and a melt viscosity at a temperature of 300 to 400 ° C. of 1.0 to 1.0 × 10 ⁵ Pa · s. Thermoplastic wholly aromatic copolymerized polyimide ester. 2. The following general formula (However, Y ¹ in the formula [I ′] is a hydrogen atom or R ¹ CO— (wherein R ¹ represents a hydrocarbon group having 1 to 18 carbon atoms), and Z ¹ is hydrogen. An atom or a hydrocarbon group having 1 to 18 carbon atoms) [I '] represented by the following general formula (However, Y ² in the formula [II ′] is a hydrogen atom or R ² CO—, and Y ³ is a hydrogen atom or R ³ CO—. Here, R ² and
R ³ represents a hydrocarbon group having 1 to 18 carbon atoms. ) And a compound of the following general formula (However, Z ² and Z ³ in the formula [III ′] are a hydrogen atom or a hydrocarbon group having 1 to 18 carbon atoms, and the —COOZ ² group and the —COOZ ³ group are mutually para-position or meta-position of the benzene ring. Compound [III ′] represented by the following general formula (Provided that Z ⁴ and Z ⁵ in the formula [IV ′] are hydrogen atoms or a hydrocarbon group having 1 to 18 carbon atoms.] [I ′] is 20 to 90 mol%, [II '] 5-40 mol%, [III'] 1.0-39.9 mol%, [IV '] 0.1-4.0 mol%, [III'] +
5 to 40 mol% of [IV '], [II'] / ([III '] + [I
V ′]) is reacted at a molar ratio of (10/11) to (11/10), and the following general formula Y ^p —O—Z ^q [V ′] (in the formula [V ′] Y ^p represents Y ¹ , Y ₂ or Y ³ , and Z ^q represents Z ¹ , Z ² , Z ³ , Z ⁴ or Z ⁵ ). The method for producing a wholly aromatic copolymerized polyimide ester according to claim 1, which is separated. 3. The following general formula (However, Y ¹ in the formula [I ′] is a hydrogen atom or R ¹ CO— (wherein R ¹ represents a hydrocarbon group having 1 to 18 carbon atoms), and Z ¹ is hydrogen. An atom or a hydrocarbon group having 1 to 18 carbon atoms) [I '] represented by the following general formula (However, in the formula [II ′], Y ² is a hydrogen atom or R ² CO—, and Y ³ is a hydrogen atom or R ³ CO—. Here, R ² and
R ³ represents a hydrocarbon group having 1 to 18 carbon atoms. ) And a compound of the following general formula (However, Z ² and Z ³ in the formula [III ′] are a hydrogen atom or a hydrocarbon group having 1 to 18 carbon atoms, and the —COOZ ² group and the —COOZ ³ group are mutually para-position or meta-position of the benzene ring. Compound [III ′] represented by the following general formula (However, Z ⁴ and Z ⁵ in the formula [IV ″] are a hydrogen atom or a hydrocarbon group having 1 to 18 carbon atoms, and the —COOZ ⁴ group and the —COOZ ⁵ group are in the para position or meta to the amide group. The compound [IV ″] represented by the formula
I ′] is 5 to 40 mol%, [III ′] is 1.0 to 39.9 mol%,
[IV ″] is 0.1 to 4.0 mol%, and [III ′] + [I
V ″] is 5 to 40 mol%, [II ′] / ([III ′] + [I
V ″]) is reacted at a molar ratio of (10/11) to (11/10), and imide cyclization of the compound [IV ″] and the following general formula Y ^p —O—Z ^q [V ′ (However, Y ^p in the formula [V ′] represents Y ¹ , Y ² or Y ³ and Z ^q represents Z ¹ , Z ² , Z ³ , Z ⁴ or Z ^5. ) The method for producing a wholly aromatic copolymerized polyimide ester according to claim 1, wherein the represented compound [V '] is eliminated.